Synthesis, Structures, and Oxidation of Iridium(III) Alkyl Compounds Containing Thiolate and Dithiolate Ligands

Autor: Wai Yeung Wong, Wa-Hung Leung, Qian-Feng Zhang, Ka Wang Chan, Ian D. Williams, Yiu Keung Sau
Rok vydání: 2008
Předmět:
Zdroj: European Journal of Inorganic Chemistry. 2008:4353-4359
ISSN: 1099-0682
1434-1948
DOI: 10.1002/ejic.200800460
Popis: Treatment of [Ir(dtbpy){CH 2 CMe 2 C c 6 H 4 (Ir-C c )}(C 6 H 4 tBu-2)] (1) (dtbpy = 4,4'-di-tert-butyl-2,2'-bipyridyl) with the dichalcogenides R 2 Q 2 in refluxing toluene afforded the chalcogenolate-bridged dinuclear complexes [Ir(dtbpy)-{CH 2 CMe 2 C c 6 H 4 (Ir-C c )}2(μ-QR)2 [RQ = pTolS (2), PhSe (3)]. Similarly, heating a solution of [Rh(dtbpy)(CH 2 CMe 2 -C c 6 H 4 (Ir-C c )}(CH2CMe2Ph)] and p-tolyl sulfide in toluene at reflux gave [Rh(dtbpy){CH 2 CM e 2 C c 6 H 4 (Ir-C c ))] 2 (μ-SpTol)2 (4). Treatment of [Ir(dtbpy)(CH2CMe2Ph)Cl] 2 (μ-Cl)2 with Na(Sxyl) (xyl = 2,6-dimethylphenyl) and Na 2 (S ^ S) afforded [Ir(dtbpy)(CH2CMe2Ph)(Sxyl)2]2 (5) and [Ir(dtbpy)-(CH 2 CMe 2 Ph)(S^S)] 2 (S^S 2- = maleonitriledithiolate (6), toluene-3,4-dithiolate (7), benzene-1,2-dithiolate (8)}. Oxidation of compound 8 with AgOTf (OTf- = triflate) resulted in dimerization of the bdt 2- ligand by S-S bond formation and the isolation of [Ir 2 (dtbpy) 2 (CH 2 Me 2 Ph) 2 {(bdt) 2 }][OTf] 2 (9). The solid-state structures of compounds 2, 3, 4, 7, and 9 were determined.
Databáze: OpenAIRE
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